Dyes derived from 1, 2-disubstituted-3, 5-pyrazolidinediones and photographic elements containing such dyes



United States Patent DYES DERIVED FROM 1,2 DISUBSTITUTED 3,5-

PYRAZOLIDINEDIONES AND PHOTDGRAPHIC ELEMENTS CONTAINING SUCH DYES PhilipW. Jenkins and Leslie G. S. Brooker, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporationof New Jersey No Drawing. Filed June 10, 1963, Ser. No. 286,449

7 Claims. (Cl. 96102) This invention is related to dyes for photographyand more particularly to dyes derived from 1,2-disuhstituted-3,5-pyrazolidinediones and their use as sensitizers for photographicsilver halide emulsions and/or bleachable filter dyes for lightabsorbing layers in photographic elements.

It is known that certain cyanine dyes are useful for spectralsensitization of silver halide emulsions, that is, for extending thesensitivity of the silver halide to light of longer wavelengths.

It is also known to use certain bleachable dyes in lightfilteringhydrophilic layers in light-sensitive photographic elements. Suchlight-filtering layers may be coated over the light-sensitive layer,between two difierently sensitized light-sensitive layers, between alight-sensitive layer and the support or on the side of the supportopposite to the side bearing a light-sensitive layer. Dyes useful forfilter layers must not only absorb light of the desired wavelengths butmust be readily bleachable and/ or removable during the normalphotographic processing operations. New sensitizing and/orlight-filtering dyes are desired for use in photographic elements.

It is therefore an object of our invention to provide a new class ofdyes derived from l,2-disubstituted-3,5- pyrazolidinediones.

A further object is to provide new cyanine, merocyanine, styryl andholopolar dyes derived from 1,2-disubstituted-3,5-pyrazolidinedionesthat are valuable for use in photographic elements.

Another object is to provide a synthesis for making our new dyes.

Another object is to provide photographic silver halide emulsionscontaining our new dyes.

Still another object is to provide photographic elements comprising asupport, at least one hydrophilic colloid layer containinglight-sensitive silver halide and at least one hydrophilic layercontaining at least one of our dyes.

Still other objects will become apparent from a consideration of thefollowing specification and claims.

These and other objects of our invention are accomplished bysynthesizing and using the dyes of our invention which are derived froma compound having the formula:

C-N-R Wherein R and R each represents the same or a different groupselected from the class consisting of alkyl groups, e.g., methyl, ethyl,phenethyl, propyl, butyl, hexyl, cyclohexyl, dodecyl, octadecyl, etc.and aryl groups, e.g., phenyl, 4-methylphenyl, 4-methoxyphenyl, etc.

Patented Apr. 23, 1968 The dyes of our invention include thoserepresented by the formulas:

wherein R and R are as defined previously; R represents an alkyl group,e.g., methyl, earbethoxymethyl, ethyl, carbethoxyethyl, carboxyethyl,propyl, butyl, 4-sulfobutyl, hexyl, dodecyl, octadecyl, etc.; or an arylgroup, e.g., phenyl, 4-methylphenyl, etc.; L and L each represents amethine or a substituted methine group (e.g., CH= or -CR where Rrepresents an alkyl group, such as methyl, ethyl, butyl, hexyl, decyl,etc.; or an aryl group, such as phenyl, tolyl, etc.); It represents aninteger of from 1 to 4; 1' represents an integer of from 1 to 3; Zrepresents the nonmetallic atoms required to complete a 5 to 6 memberedheterocyclic nucleus selected from the class of nuclei consisting ofthose of the thiazole series (e.g., thiazole, 4-methylthiazole,4-phenylthiazole, 5- methylthiazole, S-phenylthiazole,4,5-dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)thiazole,etc.), those of the benzothiazole series (e.g., benzothiazole,4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole,7-chlorobenzothiazole, 4-methylbenzothiazole, 5- methylbenzothiazole,6-methylbenzothiazole, 5 bromobenzothiazole, -bromobenzothiazole,4-phenylbenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5 iodobenzothiazole,6-iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole,tetrahydrobenzothiazole, 5,6- dimethoxybenzothiazole, 5,6dioxymethylenebenzothiazole, S-hydroxybenzothiazole, 6hydroxybenzothiazole, etc.), those of the naphthothiazole series (e.g.,u-naphthothiazole, fi-naphthothiazole, 5 methoxy-B-naphthothiazole,5-ethoXy-B-naphthothiazole, 8-methoXy-a-naphthothiazole,7-methoXy-a-naphthothiazole, etc.), those of thethionaphtheno-7,6,4,5-thiazole series (e.g.,4'-methoXythianaphtheno-7,6',4,5-thiazole, etc.), those of the oxazoleseries (e.g., 4-methyloxazole, S-methyloxazole, 4- phenyloxazole,4,5-diphenyloxazole, 4-ethyloxazole, 4,5- dimethyloxazole,-phenyloxazole, etc.), those of the benzoxazole series (e.g.,benzoxazole, S-chlorobenzoxazole, S-methylbenzoxazole,5-phenylbenzoxazole, 6-methylbenzoazole, 5,ti-dimethylbenzoxazole,4,6-dimethy1benzoxazole, S-methoxybenzoxazole, S-ethoxybenzoxazole, 5-chlorobenzoxazole, -methoxybenzoxazole, 5 hydroxybenzoxazole,6-hydroxybenzoxazole, etc.), those of the naphthoxazole series (e.g.,ot-naphthoxazole, fl-napththoxazole, etc.), those of the selenazoleseries (e.g., 4-methylselenazole, 4-phenylselenazole, etc.), those ofthe benzoselenazole series (e.g., benzoselenazole,5-chlorobenzoselenazole, 5-methoxybenzoselenazole,S-hydroxyoenzoselenazole, tetrahydrobenzoselenazole, etc.), those of thenaphthoselenazole series (e.g., u-naphthoselenazole, ,9-naphthoselenazole, etc.), those of the thiazoline series (e.g.,thiazoline, 4-methylthiazoline, etc.), those of the 2-quinoline series(e.g., quinoline, 3-methylquinoline, 5- methylquinoline,7-methylqui-noline, 8-methylquinoline, 6-chloroquinoline,8-chloroquinoline, fi-methoxyquinoline, -ethoxyquinoline,6-hydroxyquinoline, 8-hydroxyquinoline, etc.), those of the 4-quinolineseries (e.g., quinoline, 6-methoxyquinoline, 7-methylquinoline, 8methylquinoline, etc.), those of the l-isoquinoline series (e.g.,l-isoquinoline, 3,4-dihydro-l-isoquinoline, etc.), those of the3-isoquinoline series (e.g., 3-isoquinoline, 6-methyl-3-isoquinoline,etc.), those of the 3,3-dialkylindolenine series (e.g.,3,3-dimethylindolenine, 3,3,S-trimethylindolenine,3,3,7-trimethylindolenine, etc.), the pyridine series (e.g., Z-pyridine,4-pyridine, S-methyl-Z-pyridine, etc.), those of the imidazole series(e.g., imidazole, 1-ethyl-4-phenylimidazole, 4,5-dimethylimidazole,etc.), those of the benzimidazole series (e.g., benzimidazole,1-butyl-4-methylbenzimidazole, l-ethyl 4 phenylbenzimidazole,4,5-dichlorobenzimidazole, etc.), and those of the naphthimidazoleseries (e.g., l-methyl-a-naphthimidazole, fi-naphthimidazole,S-methoXy-B-naphthimidazole, etc.); W and W each represent thenonmetallic atoms necessary to complete the same or a different 5 to 6membered heterocyclic nucleus selected from those of the thiazoleseries, the benzothiazole series, the naphthothiazole series, theoxazole series, the benzoxazole series, the naphthoxazole series, theselenazole series, the benzoselenazole series, the naphthoselenazoleseries, the thiazoline series, the 2- quinoline series, the 4-quinolineseries, the l-isoquinoline series, the 3-isoquinoline series, the3,3-dialkylindolenine series, and the pyridine series all as describedwith illustrative examples for Z, however, W and W do not include thenuclei of the imidazole series, the benzimidazole series or thenaphthimidazole series; R and R each represents the same or a differentalkyl group, e.g., methyl, ethyl, Z-cyanomethyl, propyl, butyl, hexyl,octadecyl, etc.; and m represents an integer of from 1 to 2; and p and qeach represent an integer from 1 to 2.

Our dyes are valuable for use in photographic elements. Certain of thedyes have sensitizing properties for silver halide emulsions whileothers are easily bleachable by photographic processing solutions andcan therefore be used in the preparation of bleachable filter orantihalation layers. Some of our dyes are useful in filter layers coatedover the light-sensitive layer(s) or between two or more light-sensitivelayers which may be differently sensitized as in elements for colorphotography.

In general the dyes of our invention are produced to advantage byheating the l,2-disubstituted-3,S-pyrazolidinedione or its 4-substitutedderivative with the appropriate intermediate in a suitable inertsolvent, preferably in the presence of a basic condensing agent. Thecondensation reactions are carried out to advantage by heating thereaction mixture to a temperature between room temperature and thereflux temperature. These conditions are used in the following generalsyntheses.

Any of the well known basic condensing agents are used, such as thetrialkylamines, e.g., triethylamine, tri-Il- 4 propylamine,triisopropylamine, tri-n-butylamine, etc., the N,N-dialkylanilines,e.g., N,N-dimethylaniline, N,N-diethylaniline, etc., theN-alkylpiperidines, e.g., N-methylpiperidine, N-ethylpiperidine, etc.

VI .Z a

wherein R, p and Z are as described previously, Y represents a group,such as ethyl (to produce a simple merocyanine), fi-acetanilidovinyl orthioacetonylidene (to produce a merocarbocyanine), or4-methoxybutadienyl, or 4-anilinovinyl-1,3-butadienyl (to produce amerodicarbocyanine dye), and X- represents any acid anion, e.g.,chloride, bromide, methylsulfate, ethylsulfate, p-toluenesulfonate,perchlorate, etc. The Y group can also be methyl when4-(5-acetanilido-2,4-pentadienylidine)-l,2-substituted-3,S-pyrazolidinedione isused in the condensation reaction.

The oxonols of Formula III are prepared to advantage by condensing theappropriate compound of Formula I with diethoxymethyl acetate (to give amonomethinoxonol), trimethoxypropene (to give 'a trimethinoxonol) and1-anilino-5-phenylimino-1,3-pentadiene hydrochloride (to give apentamethinoxonol).

The holopolar dyes of Formula IV are prepared to advantage by condensingthe appropriate compound of Formula I with a compound represented by theformula:

wherein R p, q, W, W and X 'are as defined previously and R representsan alkyl group or an aryl group.

The styryl dyes of Formula V are prepared to advantage by condensing acompound of Formula I with an intermediate such asp-dimethyl'aminobenzaldehyde or p-dimethylaminocinnamaldehyde. No basiccondensing agent is needed for these reactions.

The intermediates of Formulas VI, VII and the others used (to condensewith our new intermediate of Formula I) are known in the art and neednot be described further.

The following representative dyes 'and their syntheses will serve toillustrate but not limit our invention.

Dye 1.4-(3-ethyl-2-benzothiazolinylidene)-1,2-diphenyl-3,5-pyrazolidinedione 1,2-diphenyl-3,S-pyrazolidinedione (1mol., 2.5 g.), 3-ethyl-2-ethylthiobenzothiazolium ethylsulfate (1 mol.,3.6 g.), and triethylamine (1 mol., 1.0 g.) were dissolved in ethanol(25 ml.), and the solution was heated under reflux for fifteen minutes.The mixture was chilled overnight, and the crude product was isolated byfiltration, washed with methanol, and dried. After tworecrystallizations from pyridine and methanol, the yield of pure dye was1.95 g. (47%), M.P. 249.0-250.5 C.

I o-1rnn C-NPl u 1 1,2-diphenyl-3,5-pyrazolidinedione (1 mol., 2.5 g.),1-ethyl-2-ethylthionaphtho[1,2-d]thiazolium ethylsulfate (1 mol., 4.1g.), and triethylamine (1 mol., 1.0 g.) were dissolved in ethanol (35ml.), and the solution was heated under reflux for fifteen minutes. Themixture was chilled overnight, and the crude product was isolated byfiltration, washed with methanol, and dried. After tworecrystallizations from pyridine and methanol, the yield of pure dye was3.2 g. (69% IM.P. 251.0253.0 C.

Dye 3 .4-[ 1,3,3-trimethyl-Z-indolinylidene ethylidene]-1,2-diphenyl-3,5-pyrazolidinedione Me Me 01,2-diphenyl-3,5-pyrazolidinedione (1 mol., 1.25 g.),2-B-acetanilidovinyl-1,3,3-trin1ethyl-3H indolium iodide (1 mol., 2.25g.), and triethylamine (1 mol., 0.5 g.) were dissolved in ethanol ml.and the solution was heated under reflux for twenty-five minutes. Themixture was chilled overnight, and the crude product was isolated byfiltration, washed with methanol, and dried. After tworecryst'allizations from pyridine and methanol, the yield of pure dyewas -1.4 g. (64%), M.P. 272.5274.0 C. dec.

Dye 4.4-[(3-ethyl-2-benzoxazolinylidene)ethylidene]- 1,2-dimethyl-3,5-pyrazolidinedione 1,2-dimethyl-3,5-pyrazolidinedione (1 mol., 0.45 g.),2-fl-acetanilidovinyl-3-ethylbenzoxazolium iodide (1 mol., 1.45 g.), andtriethylamine (1 mol., 0.35 g.) were dissolved in ethanol (10 ml.), andthe solution was heated under reflux for twenty minutes. The mixture waschilled overnight, and the first crop of crude product was isolated byfiltration, washed with methanol, and dried. The mother liquor andwashes were combined and concentrated to dryness under reduced pressure.The residue was taken up in methanol (10 ml.), and the solution wasdiluted with water (100 ml.). After chilling, the second crop of productwas isolated by filtration and dried. The two crops of product werecombined, and after two recrystallizations from methanol and water, theyield of pure dye was 0.6 g. (60%), M.P. 243.0244.5 C. dec.

Dye 5,-4 (3-ethyl-2-benzothiazolinylidene ethylidene] 1,2-diphenyl-3 ,5-pyrazolidinedione 1,2-diphenyl-3,5-pyrazolidinedione (1 mol., 1.25 g.),2- fl-acetanilidovinyl-3-ethylbenzothiazolium iodide (1 mol.,

2.25 g.), and triethylamine (1 mol., 0.5 g.) were dissolved in ethanol(25 ml.), and the solution was heated under reflux for twenty minutes.The mixture was chilled overnight, and the crude product was isolated byfiltration, washed with methanol, and dried. After tworecrystallizations from pyridine and methanol, the yield of pure dye was2.1 g. M.P. 2595-2605 C. dec.

Dye 6.-4-(3-ethyl-2-benzothiazolinylidene)isopropylidene]-1,2-diphenyl-3,5-pyrazolidinedione3-ethyl-2-thioacetonylidenebenzothiazoline (1 mol., 2.4 g.) and methylp-toluenesulfonate (1 mol., 1.9 g.) were mixed and heated on a steambath for one hundred minutes. The resulting solid cake was ground to afine powder under ether. The mixture was filtered, and the precipitatewas washed with ether. This precipitate together with1,2-diphenyl-3,5-pyrazolidinedione (1 mol., 2.5 g.) and triethylamine (1mol., 1.0 g.) was dissolved in ethanol (25 ml.), and the solution washeated under reflux for twenty minutes. The mixture was chilledovernight, and the crude product was isolated by filtration, washed withmethanol, and dried. After two recrystallizations from pyridine andmethanol, the yield of pure dye was 3.7 g. (82%), M.P. 287.0289.0 C.dec.

Dye 7.4-[(1-ethyl-2-naphtho[1,2-d]thiazolinylidene) ethylidene] l,2-dimethyl-3,S-pyrazolidinedione 1,2-dimethyl-3,S-pyrazolidinedione (1mol., 0.45 g.), 2- B-anilinovinyl- 1-ethylnaphtho[ 1,2-d] thiazoliump-toluenesulfonate (1 mol., 1.7 g.), acetic anhydride (1 mol.+%, 0.65g.), and triethylamine (1 mol.+100%, 1.00 g.) were dissolved in ethanol(10 ml.), and the solution was heated under reflux for twenty minutes.The mixture was chilled overnight, and the crude product was isolated byfiltration, washed with methanol, and dried. After tworecrystallizations for methanol, the yield of pure dye was 0.7 g. (57%),M.P. 295.5297.0 C. dec.

Dye 8.4-[ 1-ethyl-2-naphtho[ 1,2-d] thiazolinylidene) isopropylidene]-l,Z-dimethyl-3,5-pyrazolidinedione1-ethyl-2-thioacetonylidenenaphtho[1,2-d]thiazoline (1 mol., 2.85 g.)and methyl p-toluenesulfonate (1 mol., 1.85 g.) were mixed and heated ona steam bath for forty minutes. This crude product together with1,2-dimethyl- 3,5-pyrazolidinedione (1 mol., 1.30 g.) and triethylamine(1 mol., 1.0 g.) was dissolved in ethanol (30 ml.), and the solution washeated under reflux for twenty minutes. The mixture was chilledovernight, and the crude roduct was isolated by filtration, washed withmethanol, and dried. After two recrystallizations from pyridine and 7methanol, the yield of pure dye was 2.35 g. (62% M.P. 264.0265.0 C. dec.

Dye 9.--4[ l-ethyl-2( lH)-quinolylidene ethylidene] 1,2-diphenyl-3 ,5-pyrazolidinedione l,Z-diphenyl-S,5'pyrazolidinedionc (1 mol., 2.5 g),2- 8-aniiinovinyl-l-ethylquinolinium iodide (1 mol., 4.0 g.), aceticanhydride (1 mol.+100%, 2.0 g.), and triethylamine (1 mol., 2.0 g.) weredissolved in ethanol ml.), and the solution was heated under reflux fortwenty minutes. The mixture was chilled overnight, and the crude productwas isolated by filtration, washed with methanol, and dried. After tworecrystallizations from pyridine and methanol, the yield of pure dye was2.05 g. (47%), M.P. 27l.5-273.0 C. dec.

Dye 10.--4-[ (1-ethyl-4(1H)-quinolylidene)ethylidene]-1,2-diphenyl-3,5-pyrazolidinedione i C-NPh1,2-diphenyl-3,5pyrazolidinedione (1 mol., 2.5 g.),4-fl-anilinovinyl-l-ethylquinolinium iodide (1 mol., 4.0 g.), aceticanhydride (1 mol.+100%, 2.0 g), and triethylamine (1 mol., 2.0 g.) weredissolved in ethanol (25 ml.), and the solution was heated under refluxfor twenty minutes. The mixture was chilled overnight, and the crudeproduct was isolated by filtration, washed with methanol, and dried.After two recrystallizations from pyridine and methanol, the yield ofpure dye was 2.4 g. M.P. 2880-2895 C. dec.

Dye 1 1.-4- [4- 3-ethyl-2-b enzoxazolinylidcne-2-butenylidene]-1,2-dimethyl'3 ,5 -pyrazolidinedionel,2-dimethyl-3,S-pyrazolidinedione (1 mol., 0.45 g.),2-(4-rnethoxybutadienyl)-3-ethylbenzoxazolium iodide (1 mol., 1.15 g.),and triethylarnine (1 mol., 0.35 g.) were dissolved in ethanol (10 ml.),and the solution was heated under reflux for twenty minutes. Thereaction mixture was cooled and diluted with water (200 ml.). The dyesuspension was chilled overnight, and the crude product was collected byfiltration and dried. The desired dye was extracted from the crudeproduct with boiling benzene (125 ml.). The dye was precipitated fromthe benzene solulion by the addition of ligroin ml., B.P. 100ll5 C.)and, after chilling, was isolated by filtration. After onerecrystallization from benzene and ligroin (B.P. 100- C.), the yield ofpure dye was 0.2 g. (18%), M.P. 222.5-224.5 C. dec.

Dye 12-4-[4-(3-ethyl-2-benzothiazolinylidene)-2-butenylidene]-1,2-diphenyl-3,S-pyrazolidinedione1,2-dipheny1-3,5-pyrazolidinedione (1 mol., 2.5 g.), 2-(4-anilinovinyl1,3-butadienyl)-3-ethylbenzothiazolium iodide (1 mol., 4.35 g.), aceticanhydride (1 mol.+l00%, 2.0 g.), and triethylamine (1 mol.+l00%, 3.0 g.)were dissolved in ethanol (25 ml.), and the solution was heated underreflux for twenty minutes. The reaction mixture was cooled and dilutedwith water ml.). The dye suspension was chilled overnight, and the crudeproduct was collected by filtration. This damp product was boiled with50 ml. of methanol. After chilling the mixture overnight, the methanolwas decanted and the residual gum dissolved in pyridine. This solutionwas filtered and diluted with methanol. The solution was chilled, andthe crude dye was isolated by filtration and dried. After tworecrystallizations from pyridine and methanol, the yield of pure dye was0.65 g. (14%), M.P. 225.5-227.5 C. dec.

Dye 13 .4- 6- 3-ethyl-2-benzoxazolinylidene -2,4hexadienylidene]-1,2-diphenyl-3 ,S-pyrazolidinedione 4 (5acetanilido-2,4-pentadienylidene)-1,2-diphenyl- 3,5-pyrazolidinedione (1mol., 2.25 g.), 3-ethyl-2-methylbenzoxazolium iodide (1 mol., 1.45 g.),and triethylarnine (1 mol., 0.5 g.) were dissolved in methanol (15 ml.),and the solution was heated under reflux for fifteen minutes. The crudedye was isolated from the hot reaction mixture by filtration. After onerecrystallization from cresol and methanol containing piperidine, theyield of pure dye was 0.17 g. (7%), M.P. 174.5l76.5 C. dec.

Dye 14.4-[6- 3-ethyl-2benzothiazolinylidene)-2,4-hexadienylidene]-1,2-diphenyl-3,5-pyrazolidinedione4-(5-acetanilido 2,4 pentadienylidene)-1,2-diphenyl-3,5-pyrazolidinedione (1 mol., 2.25 g.), 3-ethyl-2-methylbenzothiazoliumiodide (1 mol., 1.55 g), and triethylamine (1 mol., 0.5 g.) weredissolved in ethanol (15 ml.), and the solution was heatedv under refluxfor ten minutes. The reaction mixture was chilled, and the crude productwas isolated by filtration, washed with methanol, and dried.

After one recrystallization from pyridine and methanol, the yield ofpure dye was 1.4 g. (57%), M.P. 1410-1440 C. dec.

Dye15.-4-[1,3-di(3-ethyl-2-benzothiazolinylidene)isopropylidene]-1,2-diphenyl-3,5-pyrazolidinedioneEt I F Et t? P11 P11 3,3 diethyl 9 phenylthiothiacarbocyanine iodide (1mol., 12.0 g.), 1,2-diphenyl-3,5-pyrazolidinedione (1 mol.+10%, 5.5 g.),and triethylamine (1 mol., 2.0 g.) were dissolved in pyridine (50 ml.),and the solution was heated under reflux for twenty minutes. The hotreaction mixture was cooled and diluted with ether (400 ml.). Afterchilling the mixture overnight, the ether was decanted, and the residuewas boiled with methanol (50 ml). The mixture was chilled, and the crudeproduct was isolated by filtration, washed with methanol, and dried. Tworecrystallizations from pyridine and methanol gave 5.6 g. (46%) of agreen powder with a gold reflex, melting at 185.5187.5 (dec. at about283 C.). Two recrystallizations of a portion of this dye (1.0 g.) frombenzene gave 0.60 g. (60% recovery) of dark red crystals melting at301.0303.0 C. dec.

A second portion of this dye (1.0 g.) was recrystallized twice fromm-xylene and gave 0.45 g. (45% recovery) of dark red crystals melting at302.0304.0 C. dec.

Dye l6.4-[l,3-di(1-ethyl 2napththo{l,2-d}thiazlinylidene)-isopropylidene]-l,2-diphenyl 3,5pyrazolidinedione 3,3-diethyl 9 ethyithio4,5,4',5'-dibenzothiacarbocyanine ethylsuliate (1 mol., 3.25 g.),1,2-diphenyl-3,5- pyrazolidinedione (1 mol.+%, 1.4 g.), andtriethylamine (1 mol., 0.5 g.) were dissolved in pyridine ml.), and thesolution was heated under reflux for twenty minutes. The reactionmixture was cooled and diluted with ether (250 ml.). After chilling themixture overnight, the ether was decanted and the residue was boiledwith methanol (50 ml.). The mixture was chilled, and the crude productwas isolated by filtration, washed with methanol, and dried. After tworecrystallizations from pyridine and methanol the yield of pure dye was1.1 g. (31% MP. 290.5292.0 C. dec.

Dye 17.4-p-dimethylaminobenzylidene-1,Z-diphenyl- 3 ,5-pyrazolidinedione C-N P h 1,2-diphenyl-3,S-pyrazolidinedione (1 mol.,2.5 g.) and p-dimethylaminobenzaldehyde (1 mol., 1.5 g.) were dissolvedin ethanol ml.), and the solution was heated under reflux fortwenty-five minutes. The reaction mixture was chilled overnight, and thecrude product was isolated by filtration, washed with ethanol, anddried. After two recrystallizations from pyridine and methanol, theyield of pure dye was 3.2 g. (84% M.P. 2680-2690 C. dec.

Dye 18.-4-p-dirnethylaminocinnamylidene-1,2-diphenyl- 3 ,5-pyrazolidinedione l0 Dye 19.Bis-(1,2-diphenyl-4-pyrazolidine-3,5dione)rnethineoxonol 0 H OH O l-NR1 PhN PhI I =CH C C-NPh C it It 0 o1,2-dip henyl-3,5-pyrazolidinedione (1 mol., 5.05 g.), d'iethoxymethylacetate (1 mol.+l0%, 1.8 g.), and triethylamine (1 mol., 2.0 g.) weredissolved in ethanol (25 ml.), and the solution was heated under refluxfor fifteen minutes. The reaction mixture was cooled and diluted withglacial acetic acid (5 ml.). The solution was chilled overnight, and thecrude product was isolated by filtration and dried. After onerecrystallization from met-h'anol followed by a second recrystallizationfrom methanol containing glacial acetic acid, the yield of pure dye was1.2 g. (23%), M.P. 3l3.5-3l4.5 C. dec.

Dye 20.-Bis-( 1,2-diphenyl-4-pyrazo1idine-3,5 -dione trimethineoxonoltriethylammonium salt 1,2-diphenyl-3,S-pyrazolidinedione (1 mol., 5.05g.), trimethoxypropene (1 mol., 1.35 g.), and triethylamine (1 mol., 2.0g.) were dissolved in ethanol (25 ml.), and the solution was heatedunder reflux for fifteen minutes. The reaction mixture was chilledovernight, and the crude product was isolated by filtration and dried.After two recrystallizations from methanol, the yield of pure dye was0.9 g. (14%), M.P. 2335-2350 C. dec.

Dye 21.-Bis-(1,2-diphenyl-4-pyrazolidirie-3,S-dione) pentamet hineoxonol1,2-diphenyl-3,S-pyrazolidinedione (1 mol., 5.05 g.),l-anilino-5-phenylirnino-1,3-pentadiene hydrochloride (1 mol.,'3.1 g.),and triethyla-rnine (1 mol., 3.0 g.) were dissolved in ethanol (25 ml.),and the solution was heated under reflux for fifteen minutes. Thereaction miX- ture was chilled overnight and then diluted with glacialacetic acid (5 ml.). The solution was chilled for several additionalhours during which time ether (400 ml.) was added. The crude product wasisolated by filtration and boiled with methanol (50 ml.). The mixturewas cooled and diluted with glacial acetic acid ('1 ml.). After chillingovernight, the crude dye was isolated by filtration and dried. After onerecrystallization from methanol followed by a second recrystallizationfrom methanol containing acetic acid, the yield of pure dye was 1.15 g.(20%), MP. 2065-2085 C. dec.

1 1 Dye 22.4-(5-acetanilido Z,4-pen'tadienylidene)-1,2-diphenyl-3,S-pyrazolidinedione r11 PhN 1 c=cuon:oH-on=orr-N PhN (Die 0II It 0 U 1,2-diphenyl-3,S-pyrazolidinedionc (1 mol., 10.1 g.) and1-anilino-5-phenylamino-1,B-pentadiene hydrochloride (1 11101., 11.4 g.)were dissolved in acetic anhydride (50 ml), and the solution was heatedunder reflux for five minutes. The reaction mixture was chilledovernight, and the crude product was isolated by filtration, washed withether, and dried. The crude dye weighed 11.8 g. (65%) and was employedwithout further purification as an intermediate in the preparation ofadditional dyes. Two recrystallizations of a sample of the crude dye(2.0 g.) from glacial acetic acid containing acetic anhydride gave 1.5g. (75% recovery), M.P. 241.0242.0 C.

The 1,2-disubstituted-3,5-pyrazolidinediones were prepared byconventional methods well known in the art.

For example, the synthesis described by Jos R. Mester in Spanish Patent212,764, issued Jan. 4, 1954, has been used advantageously. This methodis abstracted in C.A., vol. 50, 8743 (1956).

In the preparation of photographic emulsions, the new dyes of theinvention are advantageously incorporated in the finished silver halideemulsion and should, of course, be uniformly distributed throughout theemulsion. The methods of incorporating dyes in emulsions are r lativelysimple and well known to those skilled in the art of emulsion making.For example, it is convenient to add the dyes from solutions inappropriate solvents, in which the solvent selected should have nodeleterious effect on the ultimate light-sensitive materials. Methanol,isopropanol, pyridine, etc. alone or in combination have provensatisfactory as solvents for the majority of our new dyes. The type ofsilver halide emulsions that are sensitized with our dyes include any ofthose prepared with hydrophilic colloids that are known to besatisfactory for dis persing light-sensitive silver halides, forexample, emulsions prepared with hydrophilic colloids, such as naturalmaterials, e.g., gelatin, albumin, agar-agar, gu'm arabic, alginic acid,etc., and synthetic hydrophilic resins, e.g., polyvinyl alcohol,polyvinyl pyrolidone, cellulose ethers, partially hydrolyzed celluloseacetate, etc.

The concentration of our new dyes in the emulsion can vary widely,-i.e., from about 5 to about 100 mgs. per liter of fiowable emulsion.The specific concentration will vary according to the type oflight-sensitive material in the emulsion and according to the effectsdesired. The most advantageous dye concentration for any given emulsioncan be readily determined by making the tests and observationscustomarily used in the art of emulsion making.

To prepare a gelatino-silver halide emulsion sensitized with one of ournew dyes, the following procedure is satisfactory: A quantity of the dyeis dissolved in a suitable solvent, and a volume of this solutioncontaining from 5 to 100 mgs. of dye is slowly added with intimatemixing to about 1000 cc. of a gelatino-silver halide emulsion. With mostof our dyes, to mgs. of dye per liter of emulsion sufiices to producethe maximum sensitizing effect with the ordinary gelatino-silvcr bromide(including bromoiodide and chlorobromide) emulsions. With fine-grainemulsions which include most of the ordinarily employed gelatino-silverchloride emulsions,

somewhat larger concentrations of dye may be necessary to secure theoptimum sensitization. While the preceding has dealt with emulsionscomprising gelatin, it will be understood that these remarks applygenerally to any emulsions in which a part or all of the gelatin issubstituted by another suitable hydrophilic colloid such as previouslymentioned.

The above statements are only illustrative and are not to be understoodas limiting our invention in any sense, as it will be apparent that ourdyes can be incorporated by other methods in many of the emulsionscustomarily used in the art. For instance, the dyes can be incorporatedby bathing a plate or film bearing an emulsion, in a solution of thedye.

Photographic silver halide emulsions, such as those listed above,containing the sensitizing dyes of our invention can also contain suchaddenda as chemical sensiiizers, e.g., sulfur sensitizers (e.g., allylthiocarbamide, thiourea, allylisothiocyanate, cystinc, etc.), variousgold compounds (e.g., potassium chloroaurate, auric trichloride, etc.)(see U.S. patents to W. D. Baldsiefen, 2,540,- 085, granted Feb. '6,1951; R. E. Damschroder, 2,597,- 856, granted May 27, 1952; and H. C.Yutzy et al., 2,597,915, granted May 27, 1952), various palladiumcompounds, such as paladium chloride (W. D. Baldsiefen, U.S. 2,540,086,granted Feb. 6, 1951), potassium chloropalladate (R. E. Staulfer et al.,U.S. 2,598,079, granted May 27, 1952), etc., or mixture of suchsensitizers; antifoggants, such as ammonium chloroplatinate (A. P. H.Trivelli et al., U.S. 2,566,245, granted Aug. 28, 1951), ammoniumchloroplatinite (A. P. H. Trivelli et al., U.S. 2,566,263, granted Aug.28, 1951)., benzotriazole, nitrobenzimidazole, S-nitroindazole,benzidine, mercaptans, etc. (see Me es, The Theory of the PhotographicProcess, Macmillan Pub., 1942, p. 460), or mixtures thereof; hardeners,such as formaldehyde (A. Miller, U.S. 1,763,- 533, granted June 10,1930), chrome alum. (U.S. 1,763,- 533), glyoxal (J. Brunken, U.S.1,870,354, granted Aug. 9, 1932), dibromacrolein (0. Block et al., GreatBritain 406,750, accepted Mar. 8, 1934), etc.; color couplers, such asthose described in I. F. Salminen et al., U.S. Patent 2,423,730, grantedJuly 7, 1947; Spence and Carroll, U.S. Patent 2,640,776, issued June 2,1953, etc; or mixtures of such addenda. Dispersing agents for colorcouplers, such as those set forth in U.S. patents to E. E. Jelley etal., 2,322,027, granted June 15, 1943, and L. D. Mannes et al.,2,304,940, granted Dec. 15, 1942, can also be employed in theabove-described emulsions.

Our emulsions are coated to advantage on any of the materials used forphotographic elements including, for example, paper, glass, celluloseacetate, cellulose nitrate, synthetic film-forming resins, etc.

The following example will serve to further illustrate our invention byshowing the sensitizing effects of representative dyes of our inventionon silver halide emulsions.

Example 1 The representative dyes of our invention were each added, insensitizing amounts ranging from about 20 mg. to about 170 mg. per moleof silver halide, to individual portions of a gelatino-silverbromoiodide emulsion containing 0.77 mole percent of silver iodide or asilver chlorobromide emulsion containing 40 mole percent of silverbromide (both of which are described by Trivelli and Smith, PhotographicScience, vol. 79, 330 (1939)). After digesting for 10 minutes at C., theemulsions were coated on a cellulose acetate support and dried. A sampleof each coating was exposed on an IB sensitometer and to a wedgespectrogram. The exposed coatings were photographically developed forthree minutes in a conventional developer solution, fixed with aconventional fixing bath, washed and dried. The sensitizing ranges andsensitizing maxima determined from the processed images are recordedwith the dye and type of emulsion.

Certain of 'our dyes, for example, dyes ll, 13, l7, 18, 19, 20 and 21are bleached by photographic developer solutions and are thereforeuseful as dyes for light-filtering layers in photographic elements.

Certain dyes of our invention derived from1,2-disubstituted-3,S-pyrazolidinediones are valuable spectralsensitizers for photographic silver halide emulsions and photographicelements coated therefrom. The preferred sensitizers include themerocyanines, holopolar dyes, and oxonols. Other dyes of our inventionare bleachable by photographic developers and find use as filter dyes inphotographic elements.

The invention has been described in considerable detail with particularreference to certain preferred embodiments thereof, but it will beunderstood that variations and modifications can be effected within thespirit and scope of the invention as described hereinabove and asdefined in the appended claims.

We claim:

1. A dye selected from those having the formulas:

wherein R and R each represent a group selected from the classconsisting of an alkyl group and an aryl group; R represents a groupselected from the class consisting of an alkyl group and an aryl group;L and L each represent a methine group; r represents an integer of from1 to 3; and W and W each represent the nonmetallic atoms required tocomplete a 5 to 6 membered heterocyclic nucleus selected from nuclei ofthe class consisting of nuclei of the thiazole series, nuclei of thebenzothiazole series, nuclei of the naphthothiazole series, nuclei ofthe thionaphtheno-T,6',4,5-thiazole series, nuclei of the oxazoleseries, nuclei of the benzoxazole series, nuclei of the naphthoxazoleseries, nuclei of the selenazole series, nuclei of the benzoselenazoleseries, nuclei of the naphthoselenazole series, nuclei of the thiazolineseries, nuclei of the 2- quinoline series, nuclei of the 4-quinolineseries, nuclei of the l-is-oquinoline series, nuclei of the3-isoquinoline series, nuclei of the 3,3-dialkylindolenine series,nuclei of the pyridine series, and q represents an integer of 1-2; R

and R represent alkyl groups and m represents an integer from 1 to 2.

2. A dye of claim 1 having Formula I.

3. A dye of claim 1 having Formula II.

4. The dye bis-(1,2-diphenyl-4-pyrazolidine-3,S-dione)pentamethineoxonol.

5. A light-sensitive photographic emulsion comprising a hydrophiliccolloid, silver halide and a dye selected from those having theformulas:

wherein R and R each represents a group selected from the classconsisting of an alkyl group and an aryl group; R represents a groupselected from the class consisting of an alkyl group and an aryl group;L and L each represent a methine group; r represents an integer of from1 to 3; and W and W each represent the nonmetallic atoms required tocomplete a 5 to 6 membered heterocyclic nucleus selected from nuclei ofthe class consisting of nuclei of the thiazole series, nuclei of thebenzothiazole series, nuclei of the naphthothiazole series, nuclei ofthe thionaphtheno-7',6',4,5-thiazole series, nuclei of the oxazoleseries, nuclei of the benzoxazole series, nuclei of the naphthoxazoleseries, nuclei of the selenazole series, nuclei of the benzoselenazoleseries, nuclei of the naphthoselenazole series, nuclei of the thiazolineseries, nuclei of the 2- quinoline series, nuclei of the 4-quinolineseries, nuclei of the l-isoquinoline series, nuclei of the3-isoquinoline series, nuclei of the 3,3-dialkylindolenine series,nuclei of of the pyridine series, and q represents an integer of 12; Rand R represent alkyl groups and m represents an integer from 1 to 2.

'6. A photographic element comprising a support, at least onehydrophilic colloid layer containing light-sensitive silver halide andat least one hydrophilic colloid layer containing a dye selected fromthose having the formulas:

wherein R and R each represents a group selected from the classconsisting of an alkyl group and an aryl group; R represents a groupselected from the class consisting of an alkyl group and an aryl group;L and L each represent a methine group; 2' represents an integer of from1 to 3; and W and W each represent the nonmetallic atoms required tocomplete a 5 and 6 rnernbered heterocyclic nucleus selected from nucleiof the class consisting of nuclei of the thiazole series, nuclei of thebenzothiazole series, nuclei of the naphthothiazole series, nuclei ofthe thionaphtheno-7',6',4,S-thiazole series, nuclei of the oxazolesen'es, nuclei of the benzoxazole series, nuclei of the naphthoxazoleseries, nuclei of the selenazole series, nuclei of the benzoselenazoleseries, nuclei of the naphthaselenazole series, nuclei of the thiazolineseries, nuclei of the 2-quinoline series, nuclei of the 4-quinolineseries, nuclei of the l-isoquinoline series, nuclei of the3-isoquinoline series, nuclei of the 3,3-dialkylinclolenine series,nuclei of the pyridine series, and q represents integer of 16 12; R andR represent alkyl groups and m represents an integer from 1 to 2.

7. A light-sensitive photographic emulsion comprising a hydrophiliccolloid, silver halide, and the dye bis- (1,2-diphenyl 4pyrazolidine-3,5-dione)pentamethineoxonol.

References Cited UNITED STATES PATENTS 2,272,163 2/ 1942 Kendall 96-1022,427,911 9/1947 Kendall et a1. 260-310 2,639,282. 5/1953 Sprague et al.96-102 2,895,955 7/1959 Haseltine et al. 260-2405 2,984,664 5/1961 Fryet a1 260-2405 2,955,939 10/1960 Brooker et al. 96-105 2,965,486 12/1960Brooker et a1. 96-105 FOREIGN PATENTS 781,551 8/1957 Great Britain.

OTHER REFERENCES Cardani et al., Faernaco, Ed. Sci. vol. XI, pp. 336-345(1956).

Zenno, Chemical Abstracts, vol. 48, pp. 11063-4 (1954).

J. TRAVIS BROWN, Primary Examiner.

NORMAN G. TORCHIN, Examiner.

5. A LIGHT-SENSITIVE PHOTOGRAPHIC EMULSION COMPRISING A HYDROPHILICCOLLOID, SILVER HALIDE AND A DYE SELECTED FROM THOSE HAVING THE FORMULA: